EP3217956B1 - Compositions having improved spf and/or water resistance - Google Patents

Compositions having improved spf and/or water resistance Download PDF

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Publication number
EP3217956B1
EP3217956B1 EP15871166.3A EP15871166A EP3217956B1 EP 3217956 B1 EP3217956 B1 EP 3217956B1 EP 15871166 A EP15871166 A EP 15871166A EP 3217956 B1 EP3217956 B1 EP 3217956B1
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EP
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Prior art keywords
acrylate
composition
polymer
particles
weight
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EP15871166.3A
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German (de)
English (en)
French (fr)
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EP3217956A4 (en
EP3217956A1 (en
Inventor
Susan Halpern Chirch
Anthony DIAZ-SANTANA
Anne-laure Suzanne BERNARD
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LOreal SA
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LOreal SA
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Priority claimed from US14/575,636 external-priority patent/US9642791B2/en
Priority claimed from US14/575,419 external-priority patent/US10512601B2/en
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Publication of EP3217956A4 publication Critical patent/EP3217956A4/en
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/30—Characterized by the absence of a particular group of ingredients
    • A61K2800/31—Anhydrous
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns

Definitions

  • the present invention is related to compositions containing at least one sunscreen active agent and having improved SPF and/or water resistance properties.
  • WO-A1-2012/072774 is related to acrylic emulsion polymers, to aqueous dispersions of said acrylic emulsion polymers and to the use of said acrylic emulsion polymers in cosmetic compositions such as hair care and hair styling preparations.
  • Said hair care preparations may contain one or more light screening agents.
  • JP-A-H10-218750 discloses a sunscreen cosmetic composition
  • a sunscreen cosmetic composition comprising a non-aqueous polymer dispersion obtained by dispersing a polymer in an organic solve and a UV light absorbent and/or a UV light scattering agent.
  • the polymer may be a polymer of an acrylate ester, a methacrylate ester, a vinyl group containing silicone, or a vinylidene group-containing silicone.
  • US-A1-2011/0243864 discloses a dispersion of polymer particles in a liquid carbon-based medium, said particles having a flexible polymeric core and being surface-stabilized with a block stabilizing polymer comprising at least one block that is insoluble in said carbon-based medium.
  • the polymer forming the polymeric core may be a polymer of an acrylate or methacrylate monomer.
  • Said document also relates to cosmetic compositions comprising said dispersion.
  • the present invention also relates to emulsion compositions for keratinous materials (for example, hair or skin) comprising at least one sunscreen active agent and at least one dispersion of acrylic polymer particles.
  • the composition is in the form of a water-in-oil (W/O) emulsion.
  • the present invention also relates to anhydrous compositions for keratinous materials (for example, hair or skin) comprising at least one sunscreen active agent and at least one dispersion of acrylic polymer particles.
  • Volatile as used herein, means having a flash point of less than about 100°C.
  • “Physiologically acceptable medium” is means a medium that is compatible with human keratin materials, for instance the skin, the lips, the nails, the eyelashes, the eyebrows or the hair.
  • compositions containing at least one sunscreen active agent are provided.
  • the sunscreen active agent(s) present in the compositions of the present invention can be organic sunscreen active agents and/or an inorganic sunscreen active agents (for example, physical blockers such as zinc oxide).
  • the sunscreen active agent(s) present in the compositions of the present invention can be soluble in water, soluble in non-aqueous material, and/or insoluble.
  • the sunscreen active agents are organic sunscreen active agents.
  • combinations of two or more sunscreens are used.
  • Organic sunscreens useful herein include anthranilates; cinnamic derivatives; dibenzoylmethane derivatives; salicylic derivatives; camphor derivatives; triazine derivatives, such as those disclosed in Patent Applications U.S. Pat. No.
  • sunscreens which are generally active in the UV-A and/or UV-B regions, denoted below under their INCI names, of:
  • Preferred inorganic sunscreens include pigments or alternatively nanopigments (mean size of the primary particles: generally between 5 nm and 100 ⁇ m, preferably between 10 nm and 50 nm) formed from coated or uncoated metal oxides, such as, for example, titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide nanopigments.
  • coated or uncoated metal oxides such as, for example, titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide nanopigments.
  • Conventional coating agents of such inorganic sunscreen active agents include alumina and/or aluminium stearate. Examples of nanopigments formed from coated or uncoated metal oxides are disclosed in particular in Patent Applications EP 518 772 and EP 518 773 .
  • Preferred UVA absorbers generally absorb radiation in the 320 to 400 nm region of the ultraviolet spectrum.
  • Examples of preferred UVA absorbers include anthranilates, benzophenones, and dibenzoyl methanes.
  • Preferred UVB absorbers generally absorb radiation in the 280 to 320 nm region of the ultraviolet spectrum.
  • Examples of preferred UVB absorbers include camphor derivatives, cinnamates, diphenylacrylates and salicylates.
  • the sunscreen active agent(s) are present in the compositions according to the invention in amounts ranging from 3 to 40% by weight with respect to the total weight of the composition, preferably ranging from about 5 to about 30% by weight with respect to the total weight of the composition, including all ranges and subranges therebetween.
  • the polymer of the particles is a C1-C4 alkyl (meth)acrylate polymer.
  • the C1-C4 alkyl (meth)acrylate monomers may be chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate and tert-butyl (meth)acrylate.
  • the monomer is a C1-C4 alkyl acrylate monomer.
  • the polymer of the particles is a methyl acrylate and/or ethyl acrylate polymer.
  • the ethylenically unsaturated acid monomer is chosen from (meth)acrylic acid, maleic acid and maleic anhydride.
  • the salts may preferably be chosen from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminium, manganese or copper; ammonium salts of formula NH4+; quaternary ammonium salts; salts of organic amines, for instance salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts.
  • the polymer of the particles may thus comprise or consist essentially of 80% to 100% by weight of C1-C4 alkyl (meth)acrylate and of 0 to 20% by weight of ethylenically unsaturated acid monomer, relative to the total weight of the polymer.
  • the polymer consists essentially of a copolymer of C1-C4 (meth)acrylate and of (meth)acrylic acid or maleic anhydride.
  • the polymer of the particles may be chosen from, for example: methyl acrylate homopolymers; ethyl acrylate homopolymers; methyl acrylate/ethyl acrylate copolymers; methyl acrylate/ethyl acrylate/acrylic acid copolymers; methyl acrylate/ethyl acrylate/maleic anhydride copolymers; methyl acrylate/acrylic acid copolymers ethyl acrylate/acrylic acid copolymers; methyl acrylate/maleic anhydride copolymers; and ethyl acrylate/maleic anhydride copolymers.
  • the polymer of the particles is a non-crosslinked polymer.
  • the polymer of the particles of the dispersion preferably has a number-average molecular weight ranging from about 2000 to about 10,000,000, preferably ranging from about 150,000 to 500,000, including all ranges and subranges therebetween.
  • the polymer of the particles are preferably present in the dispersion in a content ranging from about 21% to about 58.5% by weight, preferably ranging from about 36% to about 42% by weight, relative to the total weight of the dispersion, including all ranges and subranges therebetween.
  • the stabilizer is selected from the group consisting of isobornyl (meth)acrylate homopolymers and statistical copolymers of isobornyl (meth)acrylate and of C1-C4 alkyl (meth)acrylate present in an isobornyl (meth)acrylate/C1-C4 alkyl (meth)acrylate weight ratio of greater than 4.
  • the weight ratio ranges from about 4.5 to about 19, including all ranges and subranges therebetween.
  • the stabilizer is chosen from, for example: isobornyl acrylate homopolymers; statistical copolymers of isobornyl acrylate/methyl acrylate; statistical copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate; statistical copolymers of isobornyl methacrylate/methyl acrylate, in the weight ratio described previously.
  • the stabilizing polymer preferably has a number-average molecular weight ranging from about 10,000 to about 400,000, preferably ranging from about 20,000 to about 200,000, including all ranges and subranges therebetween.
  • the stabilizer is in contact with the surface of the polymer particles and thus makes it possible to stabilize these particles at the surface in order to keep these particles in dispersion in the non-aqueous medium of the dispersion.
  • the combination of the stabilizer + polymer of the particles present in the dispersion comprises from about 10% to about 50% by weight of polymerized isobornyl (meth)acrylate, and from about 50% to about 90% by weight of polymerized C1-C4 alkyl (meth)acrylate, relative to the total weight of the combination of the stabilizer + polymer of the particles.
  • the combination of the stabilizer + polymer of the particles present in the dispersion comprises from about 15% to about 30% by weight of polymerized isobornyl (meth)acrylate, and from about 70% to about 85% by weight of polymerized C1-C4 alkyl (meth)acrylate, relative to the total weight of the combination of the stabilizer + polymer of the particles.
  • the oily medium of the polymer dispersion comprises a hydrocarbon-based oil.
  • hydrocarbon-based oil means an oil formed essentially from, or even consisting of, carbon and hydrogen atoms, and optionally oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain, for example, alcohol, ester, ether, carboxylic acid, amine and/or amide groups.
  • the hydrocarbon-based oil may be chosen from, for example: hydrocarbon-based oils containing from 8 to 14 carbon atoms, preferably:
  • the hydrocarbon-based oil is apolar (formed solely from carbon and hydrogen atoms).
  • the hydrocarbon-based oil is preferably chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, in particular the apolar oils described previously.
  • the hydrocarbon-based oil is isododecane.
  • the dispersion according to the invention may be prepared in the following manner, which is given as an example.
  • the polymerization may be performed in dispersion, i.e. by precipitation of the polymer during formation, with protection of the formed particles with a stabilizer.
  • the stabilizing polymer is prepared by mixing the constituent monomer(s) of the stabilizing polymer, with a radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers.
  • the constituent monomer(s) of the polymer of the particles are added to the stabilizing polymer formed and polymerization of these added monomers is performed in the presence of the radical initiator.
  • the polymerization may be performed in an apolar organic solvent (synthesis solvent), followed by adding the non-volatile hydrocarbon-based oil (which should be miscible with the said synthesis solvent) and selectively distilling off the synthesis solvent.
  • synthesis solvent which is such that the monomers of the stabilizing polymer and the free-radical initiator are soluble therein, and the polymer particles obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen.
  • the synthesis solvent may be chosen from alkanes such as heptane or cyclohexane.
  • the polymerization may be performed directly in the oil, which thus also acts as synthesis solvent.
  • the monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles obtained should be insoluble therein.
  • the monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of about 5 to about 20% by weight.
  • the total amount of monomers may be present in the solvent before the start of the reaction, or part of the monomers may be added gradually as the polymerization reaction proceeds.
  • the free-radical initiator is preferably azobisisobutyronitrile or tert-butyl peroxy-2-ethylhexanoate.
  • the polymerization may be performed at a temperature ranging from about 70 to about 110°C.
  • the polymer particles are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer.
  • the stabilization may be performed by any known means, and in particular by direct addition of the stabilizer, during the polymerization.
  • the stabilizer is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles. However, it is also possible to add it continuously, especially when the monomers of the polymer of the particles are also added continuously.
  • stabilizer From about 10% to about 30% by weight, preferably from about 15% to about 25% by weight of stabilizer may be used, relative to the total weight of monomers used (stabilizer + polymer of the particles).
  • the polymer particle dispersion preferably comprises from about 30% to about 65% by weight, preferably from about 40% to about 60% by weight of solids, relative to the total weight of the dispersion.
  • the polymer of the particles is a C1-C4 alkyl (meth)acrylate polymer
  • the stabilizer is an isobornyl (meth)acrylate polymer chosen from isobornyl (meth)acrylate homopolymers and statistical copolymers of isobornyl (meth)acrylate and of C1-C4 alkyl (meth)acrylate present in an isobornyl (meth)acrylate/C1-C4 alkyl (meth)acrylate weight ratio of greater than 4.
  • the defined weight ratio makes it possible to obtain a polymer dispersion that is stable, especially after storage for seven days at room temperature (25°C).
  • the dispersions according to the invention consist of particles, which are generally spherical, of at least one surface-stabilized polymer, in a non-aqueous medium.
  • the amount of acrylic polymer particles present in the compositions of the present invention ranges from about 5 to about 50% by weight based on total weight of the composition, preferably about 7% to about 40% by weight based on the total weight of the composition, preferably about 10% to about 25% by weight based on the total weight of the composition, including all ranges and subranges therebetween.
  • the acrylic polymer particles are present in an amount effective to increase the water resistance of the composition by at least 25%, preferably by at least 30%, preferably by at least 35%, including all ranges and subranges therebetween such as, for example, 25% to 100%, 25% to 75%, 25% to 50%, 25% to 40%, and all ranges and subranges therebetween.
  • the acrylic polymer particles are present in an amount effective to increase the SPF of the composition by at least 30%, preferably by at least 100%, preferably by at least 200%, preferably by at least 300%, including all ranges and subranges therebetween such as, for example, 30% to 400%, 30% to 300%, 100% to 400%, 100% to 300%, and all ranges and subranges therebetween.
  • the acrylic polymer particles and sunscreen active agent(s) are present in the compositions and methods of the invention in a weight ratio between 3:1 and 1:3, preferably between 2:1 and 1:2, and preferably between 1.5:1 and 1:1.5.
  • more acrylic polymer particles are present than sunscreen active agent(s) on a weight basis.
  • the acrylic polymer particles and sunscreen active agent(s) are present in effective amounts to increase both SPF and water resistance properties as discussed above.
  • compositions of the present invention may also contain water.
  • water When the compositions of the present invention contain water, they are preferably in the form of an emulsion.
  • compositions of the present invention When the compositions of the present invention contain water, they can be in the form of an water-in-oil emulsion (W/O).
  • W/O water-in-oil emulsion
  • water is preferably present in an amount of from about 5% to about 50% by weight, preferably from about 10% to about 40% by weight, preferably from about 20% to about 40% by weight, including all ranges and subranges therebetween, all weights being based on the total weight of the composition.
  • compositions of the present invention when they contain water, they can also be in the form of an oil-in-water emulsion (O/W).
  • O/W oil-in-water emulsion
  • water is preferably present in an amount of from about 25% to about 80% by weight, preferably from about 30% to about 70% by weight, preferably from about 35% to about 65% by weight, including all ranges and subranges therebetween, all weights being based on the total weight of the composition.
  • compositions of the present invention may also be anhydrous (that is, contain 2% or less of water, preferably contain 1% or less of water, and preferably contain 0% water).
  • anhydrous that is, contain 2% or less of water, preferably contain 1% or less of water, and preferably contain 0% water.
  • compositions of the present invention may also include any one, or more, optional ingredients.
  • optional ingredients include, but are not limited to, co-solvents (volatile and/or non-volatile), surfactants, plasticizers, preservatives, fillers, active ingredients, colorants (pigments and/or dyes), waxes, thickening agents, film forming agents and SPF boosters.
  • compositions according to the invention are preferably intended for topical application to keratinous material such as the skin and/or hair.
  • the compositions of the present invention preferably contain a physiologically acceptable medium.
  • the components of the physiologically acceptable medium of the present invention will depend upon the intended use of the composition as one of ordinary skill in the art would understand that different cosmetic compositions generally contain ingredients useful for the specific type of composition (for example, a shampoo could contain ingredients such as surfactants, a conditioner could contain ingredients such as emollients and/or humectants, a moisturizer could contain ingredients such as emollients, moisturizers and/or active agents, and a sunscreen composition could contain ingredients such as preservatives, film forming agents and SPF boosters, among other things).
  • composition of the invention should be cosmetically or dermatologically acceptable, i.e., it should contain a non-toxic physiologically acceptable medium and should be able to be applied to the skin, superficial body growths or the lips of human beings.
  • compositions of the present invention can "comprise,” “consist of” or “consist essentially of” the identified ingredients and process steps.
  • the sole “basic and novel property” of such compositions is water resistance.
  • other water resistance enhancers for example, film forming agents
  • a "material effect" on the basic and novel property of the invention can only be an adverse effect.
  • a first step 1300 g of isododecane, 337 g of isobornyl acrylate, 28 g of methyl acrylate and 3.64 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S from Akzo) were placed in a reactor.
  • the isobornyl acrylate/methyl acrylate mass ratio is 92/8.
  • the mixture was heated at 90°C under argon with stirring.
  • the oily dispersion contains in total (stabilizer + particles) 80% methyl acrylate and 20% isobornyl acrylate.
  • the polymer particles of the dispersion have a number-average size of about 160 nm.
  • the dispersion is stable after storage for 7 days at room temperature (25°C).
  • a dispersion of polymer in isododecane was prepared according to the preparation method of Example 1, using: Step 1: 275.5 g of isobornyl acrylate, 11.6 g of methyl acrylate, 11.6 g of ethyl acrylate, 2.99 g of Trigonox 21, 750 g of isododecane; followed by addition, after reaction, of 750 g of isododecane.
  • Step 2 539.5 g of methyl acrylate, 539.5 g of ethyl acrylate, 10.8 g of Trigonox 21S, 1079 g of isododecane. After reaction, addition of 2 litres of isododecane and evaporation to obtain a solids content of 35% by weight.
  • the oily dispersion contains in total (stabilizer + particles) 40% methyl acrylate, 40% ethyl acrylate and 20% isobornyl acrylate.
  • the dispersion is stable after storage for 7 days at room temperature (25°C).
  • a dispersion of polymer in isododecane was prepared according to the preparation method of Example 1, using:
  • the oily dispersion contains in total (stabilizer + particles) 10% acrylic acid, 20% methyl acrylate, 50% ethyl acrylate and 20% isobornyl acrylate.
  • the dispersion is stable after storage for 7 days at room temperature (25°C).
  • a dispersion of polymer in isododecane was prepared according to the preparation method of Example 1, using:
  • the oily dispersion contains in total (stabilizer + particles) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate.
  • the dispersion is stable after storage for 7 days at room temperature (25°C).
  • a dispersion of polymer in isododecane was prepared according to the preparation method of Example 1, using:
  • the oily dispersion contains in total (stabilizer + particles) 10% maleic anhydride, 30% methyl acrylate, 40% ethyl acrylate and 20% isobornyl acrylate.
  • the dispersion is stable after storage for 7 days at room temperature (25°C).
  • a dispersion of polymer in isododecane was prepared according to the preparation method of Example 1, using:
  • a dispersion in isododecane of methyl acrylate polymer particles stabilized with an isobornyl methacrylate/methyl acrylate (92/8) statistical copolymer stabilizer was obtained.
  • the oily dispersion contains in total (stabilizer + particles) 80% methyl acrylate and 20% isobornyl methacrylate.
  • the dispersion is stable after storage for 7 days at room temperature (25°C).
  • oily dispersions of polymethyl acrylate stabilized with a stabilizer containing isobornyl acrylate and optionally methyl acrylate were prepared, according to the procedure of Example 1, by varying the mass ratio of isobornyl acrylate and methyl acrylate and observing the stability of the dispersion obtained as a function of the chemical constitution of the stabilizer.
  • All the dispersions comprise in total (stabilizer + particles) 80% methyl acrylate and 20% isobornyl acrylate.
  • a dispersion in isododecane of polymethyl acrylate particles stabilized with a polyisobornyl acrylate stabilizer was obtained.
  • a dispersion in isododecane of polymethyl acrylate particles stabilized with an isobornyl acrylate/methyl acrylate (85/15) statistical copolymer stabilizer was obtained.
  • the following water-in-oil emulsion composition of the present invention was prepared: Phase Chemical Name % wt/wt A Isododecane 4.74 Oil Dispersion of Example 3 21.46 Isononyl Isononanoate 5.00 Capryl Methicone 5.00 Dimethicone (2 cSt) 10.00 Polyglyceryl-4 Isostearate 0.51 Cetyl PEG/PPG-10/1 Dimethicone 1.49 Organic Sunscreen Active Agents 20.00 B Water 30.00 Disodium EDTA 0.20 Phenoxyethanol 0.20 Propylene Glycol 0.70 Chlorphenesin 0.20 Sodium Chloride 0.50
  • the emulsion composition was prepared by mixing the ingredients of phase A together and heating it to 75 to 80°C, mixing the ingredients of phase B together and heating it to 75 to 80°C, and adding phase B to phase A slowly while homogenizing using a Silverson homogenizer at 7000-8000 rpm for 15 minutes at 75 to 80°C, and then cooled.
  • Example 9 The following comparative water-in-oil emulsion composition of the present invention was prepared via the same methodology as in Example 9: Phase Chemical Name % wt/wt A Isododecane 26.20 Isononyl Isononanoate 5.00 Capryl Methicone 5.00 dimethicone (2 cSt) 10.00 Polyglyceryl-4 Isostearate 0.51 Cetyl PEG/PPG-10/1 Dimethicone 1.49 Organic Sunscreen Active Agents 20.00 B Water 30.00 Disodium EDTA 0.20 Phenoxyethanol 0.20 Propylene Glycol 0.70 Chlorphenesin 0.20 Sodium Chloride 0.50
  • Example 9 (invention)
  • Example 10 (comparative) Avg 89.23 63.80 Std. Dev. 1.17 5.95
  • Example 11 Example 12 Comparative Example 13 Avg SPF 24.12 17.71 8.48 Std Dev 3.27 4.90 1.04
  • Example 14 Example 15 Comparative Example 13 Avg SPF 34.94 31.35 8.48 Std Dev 6.67 9.02 1.04
  • Example 11 Example 12
  • Example 14 Example 15 SPF increase % 184.434% 108.844% 312.067% 269.693%

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EP15871166.3A 2014-12-18 2015-12-18 Compositions having improved spf and/or water resistance Active EP3217956B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US14/575,636 US9642791B2 (en) 2014-12-18 2014-12-18 Compositions having improved SPF
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WO2020067559A1 (ja) 2018-09-28 2020-04-02 花王株式会社 化粧料
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Family Cites Families (12)

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Publication number Priority date Publication date Assignee Title
LU85746A1 (fr) * 1985-01-28 1986-08-04 Oreal Composition cosmetique filtrante contenant un filtre uv associe a un polymere obtenu par polymerisation sequentielle en emulsion et son utilisation pour la protection de l'epiderme humain contre les radiations ultraviolettes
US5505935A (en) * 1994-05-09 1996-04-09 Elizabeth Arden Company, Division Of Conopco, Inc. Sunscreen compositions
JPH09263523A (ja) * 1996-03-29 1997-10-07 Shiseido Co Ltd 日焼け止め化粧料
JP3558247B2 (ja) 1997-02-04 2004-08-25 株式会社資生堂 日焼け止め化粧料
GB9715751D0 (en) * 1997-07-26 1997-10-01 Ciba Geigy Ag Formulations
MXPA03008714A (es) * 2002-09-26 2004-09-10 Oreal Polimeros secuenciados y composiciones cosmeticas que comprenden tales polimeros.
FR2871470B1 (fr) * 2004-06-11 2007-01-12 Oreal Copolymere a gradient, composition et procede cosmetique de maquillage ou de soin
BRPI0607038A2 (pt) * 2005-01-28 2009-12-01 Basf Ag uso de polìmeros composições cosméticas para cabelo, e para pele, e, composição dermatólogica
FR2924930A1 (fr) * 2007-12-18 2009-06-19 Oreal Emulsions photoprotectrices huile-dans-eau fluides contenant des agents tensioactifs gemines et un copolymere reticule d'acide methacrylique et d'acrylate d'alkyle en c1-c4; procede de preparation de ces emulsions
FR2937645B1 (fr) * 2008-10-24 2010-12-17 Oreal Dispersion de particules souples de polymere, compostion cosmetique la comprenant et procede de traitement cosmetique
KR101830465B1 (ko) * 2010-12-02 2018-02-20 디에스엠 아이피 어셋츠 비.브이. 아크릴계 중합체
JP5546056B2 (ja) * 2011-08-31 2014-07-09 株式会社 資生堂 油中水型乳化日焼け止め化粧料

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JP6448800B2 (ja) 2019-01-09
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WO2016100815A1 (en) 2016-06-23
EP3217956A1 (en) 2017-09-20

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